Dispersible compositions



mentednoglalw UNITED STATES PATENT OFFICE DISPERBIBIS OOIIPOBITIONBJoseph Plmnwooddown. N.J.,o-i;nortoELduPoutdeNemom-edkGampe-naWlimingtomMlmlonolDelowm No Drawing.Application August l, 1840. Serial No. 8.801

I! ll produced. when!!! thedtrormohtlotm.eeentswhichueoopehieotlohlhflizingthemteotlveuehtsoonhelddod.

to produce 1 thin ooetinzornlmotvm eoiioid on the solid when in on moonsunlinesoiutionondisnrecipitotedonthepirtieiea a the protective neat uponlddiflcotion. yieldangnimthereoteootedonthedmenedw- The invention willhe more (11117 let forth in e io'hwin: more detoiie'd descript on whichinclude: exolnpleg the: m given on flimtntive embodiments of theifivenflon and not no limitsu ns thereof. Put an expressed in put nweight unim otherwise noted.

Example I 152 pen: of m-nlimo-p-toimdine were eiurried 100% hydrochloricmid and diuotized 1n the usual woy with 68 porte of sodium nitrite at5'0.

Aeoiutionotroemsirewupreperedbydisloiflngmpertootwoodroeininiioopertdotweterondflputoofaustieoodoatflsc.

l'i'ipemotleetoooetmflidewexeeimriedin [maple m fiediemmreduinmmpilwucoumm 500 p or woter mum-m a: mm or M P with mac m on renown:

180 parts or acetoiution consisting and 252 parts oi sodium isting of300 parts d of 2000 lete, acetic alum until the pH value The slurry Theted and the slurry was Th pres cake was washed tree The dried cake was00 mesh screen and 24 parts of trisodium phosphate d thoroughly with the624 parts 0! product tained approximately 50 '7 e product was iound tobe he torn"! U found to be solubilized casein as follows: d 204 pa -L rsodium acetate. nw i were slurried in a no tion 0! the coupling thslurry was of 2000 p rts or water 0 part; bicarbonate. A solution consThe sodium roslnntc solution 6 f casein dissolved in a solution composedescribed in Example I and addparts or water and 12 parts of causticsoda Wm (or 15 minute; w oior slum added to the slurry. The temperaturwa [Late t rosim and then iusted to 25' C. and the diam solution wasslowly 11 soda. and added to the solution containing the cou lin d inExample I. The Produfil component. when coupling was comp haracteristicsto the acid was added to the Example l1 but was of the slurry wasapproximately 5.

lightly was then diluted to 1100 parts with water.

casein was thus ooaguia 16 then filtered. Bump! W of electrolyte anddried. A precipitated rosin and color press cake comwound to pass a 1osition which was isolated as described in EX- of powdered dry ry ampleI was washed thoroughly to remove the were added and mixe dried. Theground 20 around color. A yield of dlly soluble in alcohol. turwasobtained which con nic solvents ior rosin. In of coiorinz matter. Thellow color was very finely especially valuable for coloring cold waterpaints d throughout the solution. in shades of yellow. 'lhe new productwas about pecially desirable. (or the as twice as strong on an equalcolor basis a; t

d enamels as good color .same Pigment made in the cus thout thenecessity out the use .of casein. and it was into the vehicle. Othergreener and brighter in shade.

useful for the preparaand which are soluble, a0 m y be used instead otthe A c pper phthalocnnlne piz ent aste 00napecifledinmmpl'el.

described in Examp e I was coupled with beta naphthol in the tollowintmanacetanilide were siurricd in 3000 lytes and enamels in alkalinesolutions may woodrosin Example V compound prepared horn in- 117 partsof accto parts of water an Upon complc mode slight y k l e ith Causticsoda.

being required.

was prepared as isolated, washed, re

finished as describe was similar in dispersion c yellow product obtainedin reener and brighter in shade althouzh s weaker in tinting strength.

last traces o! electro dried product was rea pentine, and other orgasuch a medium the y divided and disperse Such a product is esmanuiocture or paint: an dispersions are obtainable wi or grinding thedry color resins and gums which are tion of paints and TheMil-Imnitxmp-toluidine as net:

mm d col-tine and the preparationotiairesbeeauseoritamperioretrenl 1Plfi'hichcndaum smm le w d xmmple 71!! A y powder composed of 20 partsor t-amlno- 0) am benzene was gases-n nd as described in Example I 0! U.8. P. 2,172,151 Thi dry powder Is not readily di parsed in water. Thedry p wder was dissolved in 400 parts oi water containing 5.2 parts 0!hydrochloric acid. Th solution was then run into a solution or sodiumrosinaie whic s p ep r by dissolving 80 parts of rosin in 400 parts 0!water containing 8 parts of caustic soda. Ai'ter stirring for 1 hour.the slurry was neutralized with 1.8 parts cl hydrochloric acid.filtered. and washed free oi electrolyte. The press cake was thenslurrled with 7.2 parts of caustic soda and dried. A yield of 57 partsof the dried mixture was obtained which can be ground to a tree flowingpowder which was found to be readily dis- Dcrsible in water. The productdyes acetate silk in bright shades of black when developed on the fiberwith i-hydrcxy-naphthalene-Ii-carboxylic acid in the usual manner.

Emmple II for vat dyes.

Emmple 1 12 m. of alpha naphthylamine were diamti-ted In the usualmanner. Coupling was made by slow]: adding the dlazo solution to asolution containing 13 parts of l-hydrow-naphthalene-S- sulionic acidand sodium rosinate which was prepared as follows: 20 parts cl 8 wcodrosin were dissolved in a solution consisting 0! 200 parts of water and4 parts of caustic soda with boiling. Thenthei-bydroxy-naphthalene-nllionic acid. itjpartsoi'aodaashand 8.5psrtsoisodium bicarbonate were dissolved in the solution. thisaolutionwasoooiodtoo O. and thecouplln' m madebs'addingth'edianoaoiutionovers-period of 20 minutes. pon completion of the coupling. the slurrywas made acid to blue litmus by adding 11 parts of hydrochloric acid andfiltered. The

cake was washed practically tree of elecmixcd with 6 parts oi causticThe resulting dry powder was oi 45- parts of which aPP color. Altergrinding the dry pass an 80 mesh screen. the composition wasreadilydispersible in water and suitable (or making paper beaterdyeinga, paper coatings. and for the preparation of lakes. It gavecolors in deep red or maroon shades.

The soda salt of this color is quite insoluble and is sometimes used asa pigment without conver sion to an alkaline earth salt. Because of itsinsolubility and lack oi dispersibiilty the sodaaait has heretofore beenused only in paste form for aqueous dispersions as it becomes very hardon drying. and in the dry term it Ls not suitable for use indispersions. This invention provides thecoloraaaatabledrypowderwhichisasreadilydisperaedinwateraathcpastc form of the color.

In general the processes or the invention are useful (or making d prsible subdivided 00M- tions of any type of insoluble substance. eitherorganic or inorganic which is stable to the mild alkaline and acidtreatments which are employed solids are userul extensively ascomponents or -llOUs aqueous and non-aqueous huh: and m fluidcompositions, such as insecticides. spra dyebaths containing insolubledyesmlls ior d e fabrics and for making pigmentlng compo iti containingp ment powders.

Many minor .variations in the proces which will readily suggestthemselves to those skilled in the art can be made to suit specialcircumgtan and special characteristics of the materials to be treatedFor example. in some cases It is advantageous to precipitate theinsoluble subdivided solids in the presence oi the solubllizedprotective agent and in other cases better results may be obtained byadding the solubillned protective agent to a suspension which isprepared from the predormcd subdivided solids The final products may bemade in the form of pastes or in the form of dry solids. Such productsmay or may not contain an alkaline eoiubilizing agent to convert theprotective agent to its solubilized lorm. For example, when wood rosinor its equivalent is used as the protective agent the product may b madein the form of a hydrous paste or in the dry term without adding thealkaline solubilizing agent. In the dry lorm. these products aredispersible In oreanle vehicles but not in aqueous vehicls. when analkaline soilbilizing agent is present in the paste or in the dry formoi these products, they are dispersible in aqueous vehicles but not inorganic vehicles. U casein or its equivalent isusedastheprotectiveagenttheproductsarenot dispersible in aqueouscrorganic vehicles unless the alkaline solubillzing material is added.but when the products areprepared without the solubilising agents,they'bccome dispersible in water media when metre solubilising agent isadded. The most desirable ratio of pigment to protective agent will varywith diiierent solids. In genoral, however. the optimumis that whichproduces good dispersion and good drying properties when a paste isicrmerLbnt considerable variaticn from the optimum can be made.Excessive amounts oi protective agent some poor disperaibflity and adeficiency oi the mcipitable protective agent may cause poor dryingqualitieainapaste. Theoptimum ratiooi'pigment to precipitable protectiveagent is about 1 partciaolidsandtromaboutl toaboutdparts of protectiveagent. -11 general, as low as 0.1 andashighast partsotproteotiveagenteanbe used satisfactorily. however. when a non-precipitableprotective agent is added. a deficiency pi precipitable protective agentcan be used.

Application of the new processes to susp io ci finely divided solids hasthe eiiect oi preservlog the solid particles in non-adherent term whenthe solids'are brought into'more concentrated i'orm. such as a paste.The same result is round even in those iorms where the suspendingmediuni has been removed. such as dried pastes and more or less finelydivided'agmtcs oi the dried pastes. ,The' exact manner oi'cperation oithe precipltabie protective colloids is not understoodbutitismypresentbelleithatthesuspended particiea'become coated with adim oi. the solubie form or the protective colloids, and the coatings onthe particles are preserved as unbroken films oi the protective colloidupon acidification and removal of all or the major part of thesuspending medium. In the form of pastes or solids containing alkalineagents which form soluble salts oi. the protective colloids, theparticles a e in the processes. Such dlspersibie sub-divided it stillpreserved in their original non-adherent e causeiorms and in conditionto term mpcnsions oi non-aggregated particles whenever a suspendingmedium is added. However. the invention is not limited by the suggestedtheory.

Any precipitabie protective colloid can be used instead of rosin orcasein. As a few illustrations of the many protective colloids whichproduce the results oi the invention are mentioned oxidized rosin.aryiated rosin. chlorinated rosin. nitro roslns, abietene sulionic acid,hydrogenated rosin. the naphthenic acids. Clambage. Liquid Btyrax.Guaiacum, Mastic, Myrrh. Benzoin Gum. Ammoniucsm. Oaibanum and aminoacids, such as soy bean protein. Any solubiiizlng agent which formssalts with acids and restores the protective agent upon acidificationcan be used instead oi caustic soda or trisodium phosphate, asillustrations of which are the inorganic soiubilizing agents, such assodium carbonate, potassium carbonate, potassium hydroxide. otheralkali-metal phosphates, calcium hydroxide, boron: and other alkalinereacting salts or the organic soiublliners such as triethanoiamine.

The new processes provide improved. convenient and economical means ofpreparing iinei! divided readily dispersibie particles in concenpastesand solids which are necessary to down strongly adherent aggregations 0!particles iormed during the concentration or to the original vantage ofthe invention resides in that dry, we

re-dispersc uctsareptovidedwhichmaybe -directiy dther into aqueous orinto pleagenous and Iclaim:

1. The process which particlesotaninsoiuhieaoiidin medium inthereseneeotana neousaoiuuonotawatersoluble salt at a water-insolubleprotective agent which is capable of being eonvertedfidthe protectiveagent on said removin the suspending medium and. dissolved electrolyimtii a non ed domw tion said protective the presence 0! an aqueoussoluble salt or a water-insoluble converted to the proeacess of thatwhich adhem as a articles in aqueous medium. said protective agent beingreconvertibic into a dispersion agent in q i y in excess 0! that whichthe pigment is capable oi adsorbing, acidifying the mixture to convertthe adherent water-soluble salt in a nim oi the protective agent,removing the major art 0! the aqueous medium and dissolved electrolytcs.and then adding to the aggregated particies at least suilicient of asalt-forming com pound to term a soluble salt of the adherent protectiveagent, said protective agent being present in the proportion of about0.1 part to about 9 parts per part 01 said particles.

3. The process 0! preparing disperslbie waterinsoluble particles 0! asolid which comprises mixing a suspension oi the particles in aqueousmedium with a water-soluble salt of a waterinsolubie protective agenthic i P -bio 0! being converted to the protective agent by the action ofan acid and in excess of that which adheres as a him to such particlesln aqueous medium. said protective agent being rooonvertible into adispersion agent in quantity in exces at that which the pigment iscapable 'of absorbing, acidifying the mixture to convert the adherentwater-soluble. salt-to a film oi the protective agent, removing themajorpart 01 the aqueous medium and-dissolved electrolytes. moistening theproduct thus produced with a solution containing suiiicient oi asalt-iorming compound to term a soluble salt of the protective agent,and then dryi said protective agent being present in the proportion oiabout 0.1 part to about ii parts per part 0! said particles.

4., The process at preparing dispersibie waterinsoiubie particles oi asolid which comprises mining a suspension of the particles in aqueousmedium with a water-soluble salt at a water-insoluble protective agentwhich is capable oi being converted to the protective agent by theactionofanacidandinexcessoithatwhichadheresasaiiimtosuchpartielesinaqueous medium. acidiiying the mixture toconvert the adhtrent water-soluble salt to the protective agent.removing the maior part of the aqueous medium and dissdved electrolytes.drying the product thus produced, mixing said product with sui'dcient o!a dry salt-forming compound to convert the protective agent into awater-soluble salt. and then grinding the mixture to 'a. powder.saidproteciiveagmtbeingpresentintheproportionoiahoutolparttoaboutiipartsperpartoisaidparticies.

d. Theproccsswhichcomprisesmixing intoan suspension of particles of awater-inaqueous soluble organic pigment a water-soluble salt of awater-insoluble protective agent which is capable 01 being converted tothe protective a e bytheactionoi'anacidandinexcessoithatwhichadheruasulmstosuchparticleswhentheyaresuspendedinaqueousmedium.saidprotective agmt being reoonvertihleinto a dispersion agentmquantityinucesotthatwhich the pigment is capableof adsorbing, acidifying the mixture to convert the adherentwater-soluble salt to iilms oi the protective agent on said particles.and removing the suspending medium and dissolved electrolytes until anon-suspended composition is formed. said protective agent bein presentin the proportion oi about 0.1 part toaboutipartlperpartoisaidparticles.

d. The access 0! preparing disperaibie particles of water-insolubleorganic pigments which oomprisesmixingasuspenslonoitheparticls inaqueous medium with a water-soluble salt of a water-insoluble protectiveagent which is capable of being converted to the protective agentytheactionoianaeidandinexcm orthat which adheres u a mm to suchparticles in aqueous medium, acidifying the mixture to convert theadherent water-soluble salt to the protectlve ent. removing the maiorportion of the M cous medium and dissolved electrolyte and then M 41 t0the aggregated particles sumcient oi a salt iorming compolmd to form nwatersoiibie salt 0! the protective agent. said protective agent beingpresent in the proportion oi about 0.1 part to about 9 parts per part ofsaid partials.

'l. The process 01 preparing dispersible particies of water-insolubleorganic pigments which comprises mixing a suspension oi. the particlesin aqueous medium with a water-soluble salt of a water-insolubleprotective agent which is capable of being converted to the protectiveagent by the a'ction of an acid and in excess 0! that whichadheresasanimtosuchparticiesin aqueous medium. acidiiying the mixture toequvert the adherent water-soluble salt to the protective Scent.removing the major poridon oi the aqueous medium and dissolvedelectrolytes. moistaxing the product thus produced with a solutioncontaining sumcimt of a salt-forming compound to torm a soluble salt 0!the adherent protective agent. and then drying, said protective agentbeingptcsentinthepmportionotaboutfllparttoaboutlpartaperpartotsaidparticies.

L'Ihemocessotpreparingdispenibleparticles o! Inter-insoluble organicpigments which comprises mixing a suspension of the particle in aqueousmedium with a water-soluble salt of a water-insoluble protective agentwhich is capable of being converted to the protective agent ythenctionoianaeidandinexcessodthatwhich adheres as a him to suchparticles in aqueous medium, acidifying the mixture to convert theadherent water-soluble salt to the protective particles.

tThepvocesswhichoomprisesiormingnneii adherent protective agent. saidprotective agent heingpresent-inthepcoportionoiahoutmlparttoaboutapartsperpartoisaidparticiea.

lm'lheptooeaswhiehcomprisamixingsuspen'dedparticiegctanorganicplgmentwithsodiumrosinateinaqueousmspensicmslidrosinatebdngpruentlnexceasoithatvlhichisnecessarytoiormiiimsonaaidpasticimacidiigmg the w p nslon medium untilsaid roslnnte is converted to main, and removing the suspending mediumand dissolved electrolytes until a nonsuspended composition is formed,said protective agent being present in the proportion of about 0.1 portto about 8 parts per part of said particles.

11. The process which comprises forming a precipitate of small particles0! a water-insoluble organic pigment in suspension in an aqu tousalkaline medium in the presence of sodium rosinate, said rosiuate beingpresent in excess of that which is necessary to form iiims on saidparticies, acidifying the suspension medium until the rosinate isconverted to rosin, and removing the suspending medium until anon-suspended composition is termed, said protective agent being presentin the proportion of about 0.1 part to about 9 parts per part of saidparticles.

12. The prom of preparing disperaibie particies oi water-insolubleorvanic pigments which comprises mixing a suspension 0! the particles inaqueous medium with sodium rosinate, said rosinatebeingpresentinucessoithatwhichis necessary to term films on said particles, aciditying themixture to convert the adherent watersoluble salt to the protectiveagent, removing the major portion 0! .the aqueous medium and dissolvedelectrolytes, and then adding to the aggregated particles suiiicientsodium hydroxide toconvert the rosintosodiumroslnatecaidprotcctlve agentbeing present in the proportionoil-boutmlparttoaboutflpartsperpartotaaid particles. 13; Die process atpreparing dispersihie par ticles oi water-insoluble organic pigmentswhich comprises mixing a suspension 0! the particles inaqueousmediumwithcaseingwhichhasbeen soluhiiized with an alkaline substance, saidaqlubiiined caseing being present in excess 0! thatwhichisneoessarytoiormnimsonaaidparticlec. acidifying the mixture toconvert the adherent water-soiilbie salt to the protective agent,removing the major portion 0! the aqueous medium and dissolvedelccttoiytes, and then adding to "in'the proportion of about 0.1 part toabout a being about 1 part of pigment and about 1 to about 6 parts oisaid salt and being in excess 01 that which is necessary to tom films onthe particles, acidifying the medium until said salt is converted torosin, removing the major part oi the suspending medium and dissolvedelectrolytes until a non-suspended composition is iormed, and mixing theresulting composition with at least suiiiclent oi a salt-forminginorganic compound to (arm a soluble inorganic salt oi. the adherentwood msin.

JOSEPH W. LANG.

CERTIFICATE OF comc'non.

Patent No. 25653 79.

December 19, 19141;.

JOSEPH H. LANG;

It is herehy certified that error appears in the printed specificationof the above numbered patent requiring correction as follows: Page 5,sec- 0nd column, ,ond co'lumn, lines 57 and 59, for

said Letters Patent should be read wi the record of the case in thePatent Office.

one may eonicm to Signed and sealed this 27th day of March, A. D.

.(See1) 1111029, for "sollhilizing' read --eo1ubi1izing--;

"ceasing" read --casein--; and that the page 5, seeth this correctiontherein that the Leslie Frazer Acting Commissioner of Patents.

being about 1 part of pigment and about 1 to about 6 parts oi said saltand being in excess 01 that which is necessary to tom films on theparticles, acidifying the medium until said salt is converted to rosin,removing the major part oi the suspending medium and dissolvedelectrolytes until a non-suspended composition is iormed, and mixing theresulting composition with at least suiiiclent oi a salt-forminginorganic compound to (arm a soluble inorganic salt oi. the adherentwood msin.

JOSEPH W. LANG.

CERTIFICATE OF comc'non.

Patent No. 25653 79.

December 19, 19141;.

JOSEPH H. LANG;

It is herehy certified that error appears in the printed specificationof the above numbered patent requiring correction as follows: Page 5,sec- 0nd column, ,ond co'lumn, lines 57 and 59, for

said Letters Patent should be read wi the record of the case in thePatent Office.

one may eonicm to Signed and sealed this 27th day of March, A. D.

.(See1) 1111029, for "sollhilizing' read --eo1ubi1izing--;

"ceasing" read --casein--; and that the page 5, seeth this correctiontherein that the Leslie Frazer Acting Commissioner of Patents.

